CN102504462B - Functional accessory ingredient for plastic processing and preparation method thereof - Google Patents
Functional accessory ingredient for plastic processing and preparation method thereof Download PDFInfo
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- CN102504462B CN102504462B CN 201110314895 CN201110314895A CN102504462B CN 102504462 B CN102504462 B CN 102504462B CN 201110314895 CN201110314895 CN 201110314895 CN 201110314895 A CN201110314895 A CN 201110314895A CN 102504462 B CN102504462 B CN 102504462B
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Abstract
The invention discloses a functional accessory ingredient for plastic processing and a preparation method thereof. Each raw constituent of the functional accessory ingredient is prepared in parts by weight: 90-100 parts of light calcium carbonate powder, 3-5 parts of calcined clay, 1-2 parts of calcium chloride, 1-2 parts of straw ashes, 3-5 parts of zinc oxide, 3-5 parts of fumed silica, 1-2 parts of methacrylate polymer, 1-2 parts of polyethylene wax, 1-2 parts of sodium alkyl benzene sulfonate and 1-2 parts of glycerol. The preparation method comprises the following steps: continuously oven-drying light calcium carbonate until the water content is below 0.3%, putting the calcium carbonate into a high-speed kneading machine, adding other ingredients by weight percentage, heating the mixture to 100-130 DEG C, keeping at the temperature while stirring for 8-10 min, and discharging to obtain finished products. The functional accessory ingredient for plastic processing provided by the invention reduces the surface energy among the particles and enhances compatibility and dispersity; promotes the plastication of polymer material, reduces melt viscosity, improves processing flowability, improves impact strength, rigidity, heat resistance and size stability, and has the features of energy conservation, environmental friendliness, no poison and no waste water, no waste gas and no waste residues.
Description
Technical field
The present invention relates to field of plastics processing, specifically is a kind of plastic working functional agent and preparation method thereof.
Background technology
The properties-correcting agent of China's plastic working multifunction still is in developmental stage, and is no matter bigger with external gap on kind, output, quality and modification function.
The producer that produces plastic processing modifier in the world is a lot, mainly contains U.S. Rohmandhass (ROHM AND HAAS) company and ATOCHEM company, Japanese clock deep pool chemical company etc.Rhom and Hass has developed first acrylic acid or the like impact modifier at middle nineteen sixties, serial trade mark products such as ParaloidKM323B, KM330, KM334, KM335 have been developed later in succession, wherein ParaloidKM355 is product of new generation, and superior performance is arranged.At present, Rhom and Hass has become the main provider of plastics additive in the world wide.Japan Wu Yu company is at the Pacific region and other area and Rhom and Hass's joint sales PVC impact modifier and processing aids in the world.The cooperation of above-mentioned two companies is produced ACR class properties-correcting agent in Singapore by Wu Yu chemistry (Singapore) private limited partnership, and its product grade is that the goods of ParalOidKM355P put goods on the market, and annual production is 100,000 tons.More external ACR anti-impacts change the agent trade mark and see Table 1.
The external some ACR impact modifier trades mark of table 1
Core-shell type ACR class impact modifier uses extensively, and multifunctionality is arranged, and application prospect is extensive.At present, high-performance and the most dependence on import of tailored version nuclear-shell ACR class impact modifier that China uses, minority manufacturer production such as domestic only Qilu Petrochemical, Shanxi chemical institute, Shanghai Shanhu Chemical Factory, Shanghai, and kind is single, far can not satisfy the needs of different model PVC plastics.
Different properties-correcting agent performances relatively see Table 2.
Three kinds of properties-correcting agent of table 2 relatively
Annotate: from 1 to 5, performance is from bad to excellent
In addition, except above-mentioned several impact modifying agents, also have many plastic processing functional properties-correcting agent that can be used for.For example, CPE grafting vinyl chloride multipolymer, EVA grafting vinyl chloride multipolymer, ACR grafting vinyl chloride multipolymer, EPR (second third glue) grafting vinyl chloride multipolymer, vinylchlorid grafted ethene-acrylate copolymer and EVACO multipolymer (ethane-acetic acid ethyenyl vinegar-CO terpolymer) etc.In recent years, also obtained remarkable progress with the research of two kinds of elastomer composite toughening PVCs, as with CPE/ACR, CPE/MBS composite toughening PVC.Result of study shows that the impact effect that the synergy of two kinds of toughner produces is better than single toughner.Except using elastic body toughening PVC, as using organic rigid-particle (PMMA, AS etc.), inorganic rigid particle (ultra-fine CaCO
3) report of toughening PVC, these inelastic body co-mixing systems also can be used as plastic processing modifier.Use the report of elastomerics and non-resilient composite toughening in addition, as using the ultra-fine CaCO of CPE/PS, CPE/
3, composite toughening PVC.And China PVC nanometer CaCO
3The composite study exploitation had obtained remarkable break-throughs over the past two years.
" nuclear " of ACR generally is the esters of acrylic acid rubber polymer of low cross-linking, and " shell " layer can be one deck or bilayer, so anti-impact type ACR has the branch of double-deck and three layers of " nuclear-shell " structure.Its basic process is first with letex polymerization manufactured seed emulsion particle, and appropriately crosslinked in the presence of linking agent, drips other monomers then, makes it carry out graft copolymerization on seed emulsion particle top layer.The skin of double-deck " nuclear-shell " structure ACR mainly is the multipolymer of methyl methacrylate polymer or methyl methacrylate and acrylate; Three layers of " nuclear-shell " structure ACR can be divided into time skin and outermost layer again, and secondly outer is styrene polymer often.According to the needs of using, except stratum nucleare be certainly lightly crosslinked, other layers can be divided into line style or crosslinked again.No matter double-deck or three layers of " nuclear-shell " structure ACR, the IPN that polymer chain is arranged between its stratum nucleare and the shell, so ACR is in fact again a class latex IPN, according to the mensuration of electron microscope observation and dynamic viscoelasticity spectrum instrument, all provable ACR is the heterogeneous structure system.
Its toughening mechanism is comparatively common with crazing-shear zone theoretical explanation usually.The effect of " nuclear-shell " class rubber particles on the one hand as the stress concentration center, is brought out matrix and is produced a large amount of crazings and shear zone, and the generation of its crazing or shear zone and development need to consume big energy, thereby significantly improves the shock resistance of material.Simultaneously, by bearing part three axial stresses at crazing and rubber separation surface, controlled the development of crazing, and crazing is in time stopped and unlikelyly developed into destructive crackle, the stress field at crazing tip can be brought out the generation of shear zone, and shear zone also can stop further developing of crazing.
" nuclear-shell " structure modifier, often undertaken crosslinked by the covalent linkage that adds typical cross-linking monomer, its nuclear core has good elasticity, shell is the superpolymer that has than high glass transition temperature, separates easily between particle, can be dispersed to the PVC base material uniformly, and energy and the interaction of PVC base material, thereby this class particle also plays the effect of similar ACR processing aid, promotion polyvinyl chloride resin gelation and plasticizing except can improving the PVC erosion-resisting characteristics.The major advantage of ACR class impact modifier has: good impact modification effect, wider processing temperature scope, the bloated property of low mould, product size are stablized, are had concurrently the processing aid characteristics, can shorten the fusion plastification time of compound, improve the co-mixing system moulding processability, have better weather.
Calcium carbonate belongs to the inorganic non-metallic mineral, the surface has many hydroxyls, easy adsorption moisture, the hydrophilic oleophobic of not surface treated calcium carbonate powder particle surface, be strong polarity, thereby can not with polymer organism generation chemically crosslinkeds such as plastics, rubber, in organic medium, be difficult to even dispersion, the interface is difficult to form good bonding.In addition, the calcium carbonate superfine powder particle diameter is little, have great specific surface area and higher specific surface energy, particle coalescence, reunion very easily take place in preparation and last handling process, form offspring, make grain diameter become big, in application process, lose the function that ultrafine particulate possesses, thereby influence practical application effect, can not play the effect of functional stuffing; On the contrary, can reduce some physicals of goods to a certain extent because of boundary defect.
Summary of the invention
The invention provides a kind of plastic working functional agent and preparation method thereof, prepared plastic working has reduced intergranular surface energy with functional agent, has strengthened consistency and the dispersiveness of plastics; Promote high polymer material plasticizing, reduced melt viscosity, improved processing fluidity; Improve goods shock extent, rigidity, thermotolerance and dimensional stability, have energy-saving and cost-reducing, environmental protection, nontoxic, the characteristics of not having " three wastes ".
Technical scheme of the present invention is:
A kind of plastic working functional agent is characterized in that: each feed composition is by weight than being: light calcium carbonate powder 90-100, calcinated argil 3-5, calcium chloride 1-2, stalk ashes 1-2, zinc oxide 3-5, aerosil 3-5, polymkeric substance 1-2, the polyethylene wax 1-2 of methacrylic ester, sodium alkyl benzene sulfonate 1-2, glycerine 1-2.
The described plastic working preparation method of functional agent, it is characterized in that: light calcium carbonate is dried to contain weight to moisture content be below 0.3%, add in the high speed kneader, then by weight than adding calcinated argil, calcium chloride, stalk ashes, zinc oxide, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, sodium alkyl benzene sulfonate, glycerine, after having added, be warming up to 100-130 ℃, behind the insulated and stirred 8-10min, discharging gets finished product.
Polynary composite theory refers to: can not rely on single method in modifying plastics, according to different resins, different plastics and different use occasion and different sorts, the mineral filler (powder) of different loading levels, after using properties-correcting agent, also to use one or more methods to carry out modifying plastics to reach better modification actual effect.Wherein replacing the binary compound (polymer/inorganic powder) of inorganic powder and plastics with the ternary of inorganic powder, rubber (elastomerics), plastics compound (polymkeric substance/elastomerics/inorganic powder) is main method.
Beneficial effect of the present invention: the present invention selects the tensio-active agent of multiple function to mix, reduce surface energy and the interfacial tension of particle significantly, prevent the autohemagglutination of miniaturization particle effectively, increase its consistency and dispersiveness in rubber, plastics, can promote high polymer material plasticizing, reduce melt viscosity, improve processing fluidity, improve goods shock extent, rigidity, thermotolerance and dimensional stability, thereby can realize the increment filling, reduce the goods cost.
Embodiment
A kind of plastic working functional agent, each feed composition are by weight than being: the polymkeric substance 2 of light calcium carbonate powder 100, calcinated argil 4, calcium chloride 2, stalk ashes 2, zinc oxide 4, aerosil 4, methacrylic ester, polyethylene wax 1, sodium alkyl benzene sulfonate 1, glycerine 2.
The plastic working preparation method of functional agent, light calcium carbonate dried to contain weight to moisture content be below 0.3%, add in the high speed kneader, then by weight than adding calcinated argil, calcium chloride, stalk ashes, zinc oxide, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, sodium alkyl benzene sulfonate, glycerine, after having added, be warming up to 100-130 ℃, behind the insulated and stirred 8-10min, discharging gets finished product.
Calcium carbonate modified front and back microscopic pattern compares:
Ordinary calcium carbonate particle distribution scope is wide, many forms with state of aggregation exist, though and plastic working of the present invention is more with the calcium carbonate particles amounts of particles under Electronic Speculum after functional agent-modification, but can obviously find out after surface modification treatment, surface energy is low, agglomeration does not take place, reach even dispersion, how to exist with the primary partical state, wherein part is to have (particle diameter is less than 100nm) with the nanoparticle state, thereby it can reach better dispersion in the PVC plastics, plays toughened and reinforced effect.
The calcium carbonate powder particle of plastic working of the present invention after with functional agent-modification is many to be existed with similar circle or fusiform, and such powder adds in the plastics, and is more liquid, can play toughened and reinforced effect.But the ordinary calcium carbonate powder, then surperficial corner angle are more, cause rheological poor easily, problems such as easy fracture.
Ordinary calcium carbonate and plastic working of the present invention are pressed the prescription batch mixing respectively with the calcium carbonate after functional agent-modification, and room temperature is carried out rheological experiment at PLE331 type torque rheometer after placing 8h, and the result is as shown in table 3:
Table 3 rheological experiment result
| Title | Peak torque/N.m | Balancing torque/N.r | Fusion time/S | Melt temperature/℃ |
| Common CaCO 3 | 37.4 | 25.0 | 150 | 187 |
| Modification CaCO 3 | 32.5 | 22.9 | 112 | 179 |
Prescription: 100 parts of PVC, 5 parts of one package stabilizers, 6 parts of KM355P, common CaCO
3Or modification CaCO
315 parts
As can be seen from Table 3, add modified calcium carbonate and compare with ordinary calcium carbonate, moment of torsion reduces, and fusion time obviously shortens, melt temperature descends, and plasticizing rate accelerates, and illustrates that modified calcium carbonate and PVC plastics system consistency are good, be conducive to processing, can improve extruded velocity, make the smooth exquisiteness of products appearance.This is because properties-correcting agent and the PVC plastics of modified calcium carbonate surface chemistry bonding have excellent compatibility, shows strong interior lubrication, thereby has weakened the intermolecular reactive force of PVC, makes system rheological performance change.Illustrate under equal conditions also that simultaneously modified calcium carbonate can increase loading level, also can reach good processing properties.
Calcium carbonate-filled PVC Mechanics Performance Testing before and after the modification:
PVC test piece test result compares:
With raw materials such as polyvinyl chloride resin, one package stabilizer, DOP, ordinary calcium carbonate or modified calcium carbonates, by the prescription batching, it is standby fully to mix the 10min discharging in high-speed mixer.Compound is plasticated at double roller plastic-making device, and film is abundant plasticizing 6min under 165 ℃, and hard sheet fully plastifies 8min at 190 ℃, makes the thick thin slice of 0.5mm, and room temperature cuts into dumbbell specimen test fully after transferring 24h.
Ordinary calcium carbonate and modified calcium carbonate are produced hard, soft test piece respectively, test at INSTRON 4466 type universal testing machines, the results are shown in Table 4, table 5.
Table 4 rheological experiment result
| Title | Yield strength/Mpa | Breaking tenacity/Mpa | Elongation at break/% | Young's modulus/Mpa |
| Common CaCO 3 | 50.835 | 21.364 | 46.569 | 2666.59 |
| Modification CaCO 3 | 51.995 | 44.456 | 103.365 | 2740.37 |
Prescription: 5 parts of common CaCO of 5 parts of DOP of 100 parts of one package stabilizers of PVC
3Or modification CaCO
320 parts
Table 5 soft pvc plastic test piece test result relatively
| Title | Yield strength/Mpa | Breaking tenacity/Mpa | Elongation at break/% | Young's modulus/Mpa |
| Common CaCO 3 | 7.09 | 6.91 | 48.7 | 75.7 |
| Modification CaCO 3 | 5.66 | 7.25 | 109.3 | 63.9 |
Prescription: 50 parts of common CaCO of 5 parts of DOP of 100 parts of one package stabilizers of PVC
3Or modification CaCO
3120 parts
From table 4, table 5 as can be seen, under the situation of same addition, hard, the flexible article of PVC no matter, use modified calcium carbonate, the elongation at break that the mechanical property of test piece all obviously is better than ordinary calcium carbonate, particularly test piece doubles many, and material easily plastifies, roll banding not, the surface brightness height, processing characteristics is good.This is because the ordinary calcium carbonate surface polarity is strong, and the surface energy height is easy to reunite in polyvinyl chloride resin, is difficult for disperseing, thereby influences the goods processibility, and destroy the mechanical property of goods.And modified calcium carbonate surface organic modification, surface energy significantly reduces, be difficult for reuniting, basically be to be distributed in the polyvinyl chloride resin with the primary partical state, and the molecule crane span structure effect by organic modifiers, produce strong adhesive effect at the interface, and wherein part is penetrated in the polyvinyl chloride resin three-dimensional net structure with the rigid particles that the nanometer state disperses.According to inelastic body toughening modifying viewpoint, rigidity nanometer grade calcium carbonate particle surface defective is few, the non-matching atom is many, be combined firmly with polyvinyl chloride resin, do the time spent being subjected to external force, cause matrix resin crazing absorption energy, crisp-tough transformation takes place, thereby avoid cracking of stress raisers, make matrix material reach toughened and reinforced effect, have mechanical property preferably.
Calcium carbonate after plastic working usefulness of the present invention functional agent-modification is at wave number 2979cm
-1, 2917cm
-1, 2512cm
-1, 1797cm
-1, 875cm
-1, etc. locate stretching vibration absorption band width and obviously widen, and displacement has taken place, show between the calcium carbonate after the modification to have formed firm chemical bond.
Claims (2)
1. plastic working functional agent, it is characterized in that: each feed composition is by weight than being: light calcium carbonate powder 90-100, calcinated argil 3-5, calcium chloride 1-2, stalk ashes 1-2, zinc oxide 3-5, aerosil 3-5, polymkeric substance 1-2, the polyethylene wax 1-2 of methacrylic ester, sodium alkyl benzene sulfonate 1-2, glycerine 1-2.
2. the described plastic working of claim 1 is with the preparation method of functional agent, it is characterized in that: with light calcium carbonate dry to moisture content be below 0.3% by weight, add in the high speed kneader, then by weight than adding calcinated argil, calcium chloride, stalk ashes, zinc oxide, aerosil, the polymkeric substance of methacrylic ester, polyethylene wax, sodium alkyl benzene sulfonate, glycerine, after having added, be warming up to 100-130 ℃, behind the insulated and stirred 8-10min, discharging gets finished product.
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